Catalyst compositions consisting of cobalt molybdate and various molybdate hardeners



treatment, nor from United States Patent O 3,260,682 CATALYST COMPOSITlONS COBALT MULYBDATE AND VARIGUS LYBDATE HARDENERS George Calvin, Newcastle-upo -Tyne, som, and Rowland Harris enkins, land, assignors Edinburgh, Scotland, a British company No Drawing. Filed July 30, 1964, Ser. Claims priority, application Great Britain, J an.

2,883/ 61 8 Claims. (Cl. 252-464) The present invention relates to new oxidation catalysts and is a continuation-in-part of our application Serial No. 166,673, filed January 16, 1962, now abandoned.

In our copendi-ng application Serial No. 4,221, filed January 25, 1960, is described and claimed the process for the production of acrylic or methacrylic acid by reacting at an elevated temperature in the vapor phase acrolein or methacrolein with molecular oxygen over an oxidation catalyst comprising cobalt molybdate. This catalyst gives high yields of acrylic acid from acrolein.

It is known that, after heating to a high temperature, cob-alt molybdate may on cooling undergo a spontaneous phase change, during which particulate material is disrupted to a line powder. This phenomenon, known as spalling, has been reported in the literature.

We find that our cobalt molybdate catalyst, as claimed in our copending application, Serial-No. 4,221 may occasionally show some tendency towards spalling if it has been heated to a temperature somewhat above the optimum, for example within the range 650 to 700 C. The onset of spalling is variable, and may occur rapidly on cooling to room temperature, or alternatively may only occur very slowly, during several months of storage. The tendency to spall is increased by rough handling, in which the pellets are subjected to abrasive or attrition forces, or to mechanical shock.

It is the aim of the present invention to provide a catalyst of improved physical properties, which suifers neither from spontaneous disintegration or crumbling after heat to attntion during CONSISTING OF Barrie Wood, Ep- West Ewell, Enghandling and storage.

Accordingly the present invention is an oxidation catalyst suitable for catalysing the vapor phase oxidation of unsaturated aldehydes selected from the group of acrolein and methacrolein to produce the corresponding unsaturated acids which consists essentially of cobalt molybdate having therein a minor proportion of metallic molybdate hardener selected from the group consisting of manganese, cadmium, .tin, antimony, chromium, uranium, aluminum, thorium, zirconium, and mixtures thereof heat treated to a hardness, on standard attrition test, of not more than breakdown.

The catalysts were also tested for resistance to heat by heating to a high temperature for a period of 16 hours and examining the pellets for signs of collapse.

A preferred catalyst contains manganese and/ or cadmium molybdate as hardener.

The hardener may be present in -a moderately wide range of proportions, for instance between 0.01 and 20 moles percent and preferably between 0.1 and 10 moles percent. Thehardener may be incorporated in the cobalt rnolybdate in any suitable manner for instance by coprecipitation. I

The cobalt molybdate catalyst may be prepared by mixing an aqueous solution of a cobalt salt, an aqueous solution of a salt of the metal to be incorporated as hardener, and an aqueous solution or suspension of molybdic acid or a molybdic acid salt, adding a nitrogenous base such as ammonia or an aliphatic amine for example to The Distillers Company Limited,

ethanolamine, ethylamine, triethylamine or ethylene diamine or a cycloaliphatic amine for example piperidine, or teterocyclic amines nitrogenous base compound for example hydrazine or aniline to the aqueous mixture, filtering off and subjecting the resulting precipitate to a heat treatment. The heat treatment may be merely drying off the precipitate at for example C. or preferably a drying followed by a two-stage heat .treament. After being dried the compound is subjected to a first heat treatment in air at about 350-650 C., after which the material is ground and formed into pellets.

The catalyst is then subjected to a final heat-treatment at about 500 to 650 C., preferably at about 600 C. Hard blue pellets are obtained. It is found that by use of this preferred two-stage heat treatment a harder catalyst is obtained and that the catalyst pellets have less tendency to break up through attrition.

The precipitated catalyst composition designated Blue I which is blue in color after being dried is subjected to the first heat treatment in which it undergoes a phase change to a material designated Blue II also blue in color, but which gives a different X-ray diifra-ction pattern. On grinding or pelleting of this material :there is a further phase change in color to a green or black substance depending on the state of sub-division of the particles. Heating this ground material reconverts it to the material Blue II produced after .the first heat treatment. This second heat treated material however possesses substantially increased resistance to wear, ie when the Blue 11 phase is approached from the green phase the pellets are harder than if the approach is from Blue I to Blue II.

The ratio of cobalt to molybdenum in the catalyst may vary within moderately wide limits, but it is preferred to use a molar ratio not substantially greater than 121.

The cobalt molybdate catalyst may be used as such or on a support as alumina.

Two physical tests are used to compare the hardness and stability of catalyst pellets: an attrition test (on pellets which have been given the standard heat-treatment) gives a measure of hardness and resistance to spalling under conditions of mechanical stress, and a heat treatment test (at temperatures above the standard heat-treatment temperature) shows the thermal tolerance of the pellets.

l. ATTRITION TEST 2. HEAT-TREATMENT TEST Samples of the pellets are heated for 16 hours at a series of temperatures above the optimum, usually 650 C., 700 C. and 800 C., then cooled and allowed to stand at ambient temperature for 24 hours. The pellets are then examined visually for signs of powder-formation.

The following examples, in whic all parts are by weight, are given further to illustrate the catalyst of the present invention.

Example 1 A solution of cobalt nitrate (291 parts) and manganous sulphate (22.3 parts) in water (220 parts) was heated to 60 C. and to this solution was added ammonium molyb'date (194.5 parts) in water (520 parts).

The mixture was well stirred and aqueous ammonia (5.4 N; 240 during 30 minutes, the temperature being maintained at 55-60 C pellet collapse was observed. 11 comparison a cobalt prepared in the absence of a 15 to collapsed after a heat treatment at only 650 C.

A gaseous mixture of 10% by volume of oxygen, 50% 30% by volume of steam maintained in 3.6 seconds.

Of the acrolein fed to the reactor 53% was converted to acrylic acid. The yield of acrylic acid based on acrolein consumed was 56%.

The catalyst pellets were hard. Only 0.2%

occurred during the standard attrition test,

by volume of acrolein, 10% by volume of nitrogen, and was passed over the catalyst a reactor at 400 C., the contact time being physically more robust and heating as compared with an additive free cobalt molybdate catalyst.

Example 3 of 10% by volume of acrolein, 10% by volume of oxygen, 50% by volume of nitrogen, and 30% by volume of steam was passed over the catalyst maintained in a reactor at 360 C., the contact time being 3.6 seconds.

Of the acrolein fed to the reactor 57% was converted to acrylic acid. The yield of acrylic acid based on acrolein consumed was 61%.

The catalyst showed no signs of pellet collapse after heat treatments at temperatures as high as 700 C.

4 Example 4 A cobalt molybdate catalyst was prepared as in Example 1, except that aluminum nitrate substituted for manganous sulphate.

A gaseous mixture of 10% by volume of acrolein, 10% by volume of oxygen, 50% by volume of nitrogen, and 30% by volume of steam was passed over the catalyst maintained in a reactor at 380 C., the contact time being 3.6 seconds.

Of the acrolein fed to the reactor 54% was converted to acrylic acid. The yield of acrylic acid based on acrolein consumed was 62%.

The catalyst pellets, after heat treatment at 650 C. showed no tendency to collapse, and gave only 1.8% of powder in the standard attrition test.

Example 5 at 650 C. for 16' hours. by volume of acrolein, 10% by volume of oxygen, 50% by volume of nitrogen, and 30% by volume of steam was passed over the catalyst maintained in a reactor at 382 C., the contact time being 3.6 seconds.

Of the acrolein fed to the reactor 27% was converted to acrylic acid. The yield of acrylic acid based on acrolein consumed was 44%.

The catalyst pellets were collapse even after heating physically stable and did not at 750 C. for 16 hours.

percent of chromium molybdate.

A gaseous mixture of 10% by volume of acrolein, 10% by volume of oxygen, 50% by volume of nitrogen, and 30% by volume of steam was passed over the catalyst maintained in a reactor at 360 C., the contact time being 3.6 seconds.

71%. The catalyst showed no signs of pellet collapse, even after heat treatment at temperatures to 750 C.

Example 7 A cobalt molybdate catalyst was prepared as described in Example 1 except that 3 1 parts of cadmium nitrate was with the manganous sulphate, and the quanmolybdate used was 195.8 parts.

the same double Example I, and trition test.

A gaseous mixture of 10% 10% by volume of oxygen, 50% by volume of nitrogen, and 30% steam was passed over the catalyst, maintained in a reactor at 380 C., the contact time being 3.6 seconds.

0f the acrolein fed to the reactor, 64% was converted to acrylic acid. The yield of acrylic acid based on acrolein consumed was 78%.

The catalyst showed no signs of pellet collapse after heat treatment at temperatures as high as 725 C. for 16 hours.

heat treatment procedure as described in suffered 1.2% breakdown during the atby volume of acrolein,

Example 8 The catalyst was prepared as described in Example 1 except that 50.2 parts uranyl nitrate was used instead of rnanganous sulphate, and the amount oi ammonium thorium and zirconium characterized by a standard attrition test of not more than 5% 2. An oxidation catalyst as the proportion of added molybdate is between hardness on breakdown. claimed in claim 1 wherein 0.1 and molybdate used was 194.1 parts. The cobalt molybdate 5 g 1 1 I h catalyst contained 10 mole percent of uranyl molybdate. th OX1 a g St as c 3: 1 1 6mm A gaseous mixture of 10% by volume of acrolein, 10% 6 m0 at ratio 0 co to me y ate 18 out by volume of oxygen, 50% by volume of nitrogen and the molar i p cobalt to molybdemim .about 30% by volume of steam was passed over the catalyst in th gz i catalyst as i gg m clam 1 wherem a reactor at 358 C., the contact time being 3.6 seconds 10 g 0g mangzimese i a 1 1 h Of the acrolein fed to the reactor, 57.6% was converted h f g a g y as gg c mm w erem to acrylic acid, and the yield of acrylic acid based on the t 6 m0 y ate 18 ca [mum m0 n 6. A process for the preparation of a catalyst for catacrolein consumed was 70.1%. 1 h h f 1 h The catalyst pellets subjected to a double heat treatment r a i i t i p ap ig L. if em i f at temperatures described in Example 1 were hard; the to em t e correspon mg 1 w gompnsps a mg pellets did not collapse after a heat treatment at 650 C. ammoma to an aqueous so uuon w 10 contains (1) a for 16 hours water soluble cobalt salt, (2) a salt selected from the Example 9 group consisting of water soluble salts of manganese, cadmium, tin, antimony, chromium uranium, aluminum, The Catalyst Was P p descnhed in mp 1 20 thorium and zirconium, and (3) a compound selected except that 58.8 parts of thorium nitrate was used instead f the group consisting of molybdic acid and water of mahgahous Sulphate, the amount Of ammonium y soluble salts thereof, recovering resulting precipitate and date us d wa 2 parts, and the catalyst pellets were thereafter heating said precipitate at 250 c. to 600 0., sub ected to a second heat treatment at 650 C. for 16 pelletizing, d again heating at 500 C. to 650 C. ho rs instead of 600 C- fOr 16 ur 7 A process for the preparation of a catalyst for cat- The cobalt molybdate catalyst eohtamed 10 mole P alyzing the vapor phase oxidation of acrolein or methaccent of thoflufh molybdate rolein to the corresponding acids which comprises adding 13,0503? 5531322? f 5 3? ETJ$$$ZLZTA iii b l 33 ri i t a 0 1 a watersou eco atsat,( awatersou esato manby volume of steam was passed over the catalyst in a 30 ganese, and (3) a compound selected from the group conre at the eohtaet time helhg Seeehd5- sisting of molybdic acid and water soluble salts thereof, O t e a f fed h reactor, WaS Converted recovering resulting precipitate and thereafter heating 10 i if aeld, d the ig l q aeYYhe aeld based 011 said precipitate at 250 C. to 600 C., pelletrzing, and n 6111 Consume Was again heating at 500 C. to 650 C.

The catalyst pellets were hard and withstood heat treat- 8. A process for the preparation of a catalyst for catmehts at temperatures aS hlgh as 700 alyzing the vapor phase oxidation of. acrolein or meth- Example 10 acrolein to the corresponding acids which comprises add- The catalyst was prepared as described in Example 1 mg ammlo E? to inlaqufouszsolufion i i except that 17.5 parts of stannic chloride and 61.5 parts 40 2832:2 2 5 ig iigh lg fig gg g g gg 2: of antlmonydtefiroxlde Weref used mtead gg g sisting of molybdic acid and water soluble salts thereof, fgz f 6 amount 0 ammomum m0 Y ate use recovering resulting precipitate and thereafter heating said Wag gaseou r nixture of 10% by volume of acrolein 10% g i g fi 8 8 penetlzing and agam 9 t o o by volume of oxygen, 50% by volume of nitrogen, and ea mg at o 30% by volume of steam was passed over the catalyst in References Cited by the Examine,- a reactor at 341 C., the contact time being 3.6 seconds.

Of the acrolein fed to the reactor was converted to UNITED STATES PATENTS acrylic acid, and the yield of acrylic acid based on acrolein 2,260,409 10/ 1941 Slotterbeck et al. 252 465 X consumed was 67%. 50 2,959,613 11/1960 Whitfield 260 530 X The catalyst pellets were hard, and did not collapse 2,967,820 l/ 1961 Johnson et al. 252-465 X after a heat treatment at 650 C. for 16 hours. 3,037,964 96 K ch t a1 252- 70 X We claim: F0 E G 1. An ox'dation catalyst suitable for catalyzing the R I N PA' FE NTS vapour phase oxidation of an unsaturated aldehyde 3,094,565 6/1963 Great m 3,098,102 7/ 1963 Great Britain.

selected from the group consisting of acrolein or methacrolein to produce the corresponding unsaturated acids which consists essentially of cobalt molybdate together with from 0.01 to 20 moles percent of one of the molybdates selected from the group consisting of manganese, cadmium, tin, antimony, chromium, uranium, aluminum,

OSCAR R. VERTIZ, Primary Examiner. 6O MAURICE A. BRINDISI, Examiner. G. L. OZAKI, Assistant Examiner. 

1. AN OXIDATION CATALYST SUITABLE FOR CATALYZING THE VAOUR PHASE OXIDATION OF AN UNSATURATED ALDEHYDE SELECTED FROM THE GROUP CONSISTING OF ACROLEIN OR METHACROLEIN TO PRODUCE THE CORRESPONDING UNSATURATED ACIDS WHICH CONSISTS ESSENTIALLY OF COBALT MOLYBDATE TOGETHER WITH FROM 0.01 TO 20 MOLES PERCENT OF ONE OF THE MOLYBDATES SELECTED FROM THE GROUP CONSISTING OF MANGANESE, CADMIUM, TIN, ANTIMONY, CHROMIUM, URANIUM, ALUMINUM, THORIUM AND ZIRCONIUM CHARACTERIZED BY A HARDNESS ON STANDARD ATTRITION TEST OF NOT MORE THAN 5% BREAKDOWN.
 6. A PROCESS FOR THE PREPARATION OF A CATALYST FOR CATALYZING THE VAPOR PHASE OXIDATION OF ACROLEIN OR METHACROLEIN TO THE CORRESPONDING ACIDS WHICH COMPRISES ADDING AMMONIA TO AN AQUEOUS SOLUTION WHICH CONTAINS (1) A WATER SOLUBLE COBALT SALT (2) A SALT SELECTED FROM THE GROUP CONSISTING OF WATER SOLUBLE SALTS OF MANGANESE, CADMIUM, TIN ANTIMONY, CHROMIUM, URANIUM, ALUMINUM, THORIUM AND ZIRCONIUM, AND (3) A COMPOUND SELECTED FROM THE GROUP CONSISTING OF MOLYBDIC ACID AND WATER SOLUBLE SALTS THEREOF, RECOVERING RESULTING PRECIPITATE AND THEREAFTER HEATING SAID PRECIPITATE AT 250*C. TO 600*C., PELLETIZING, AND AGAIN HEATING AT 500*C. TO 650*C. 